Treatment of hydrocarbons



Patented Mar. 1, 1949 TREATMENT OF HYDROCARBONS Glenn M. Webb, Riverside, Ill., assignor to Unlversal Oil Products Company, Chicago, 111., a

corporation of Delaware No Drawing. Application January 14, 1944,

a Serial No. 518,255

7 Claims. (01. 260683.4)

This application is a continuation-in-part of my earlier application Serial No. 489,156, filed May 31, 1943. The invention relates to a process for treating synthetic hydrocarbons produced in the presence of active fluoride catalysts to remove the small amount of organically combined fluorine present therewith as an impurity. The invention is particularly adapted to the treatment of hydrocarbons produced by the alkylation of isoparafilns with olefins using active fluoride catsuch as isobutane, isopentane, etc. with olefins,

such as propylene, butylene, amylene, etc. to produce saturated liquid hydrocarbons, utilizable as motor fuels and particularly as components in aviation gasoline, has assumed commercial importance. Active fluoride catalysts, including hydrogen fluoride or hydrofluoric acid and mixtures of hydrogen fluoride and boron fluoride, are utilized in the alkylation of isoparaflins with oleflns, but it has been found that the resultant alkylation product frequently contains minor quantities of fluorine in combination with the hydrocarbons, possibly due to the interaction of hydrogen fluoride with the oleflnic constituents of the reaction mixture under the influence of the catalyst.

Although the fluorine content of the alkylate is rarely very high, itspresence is undesirable. It has been "found that the fluorine in alkylates is definitely objectionable because of its corrosive character, its tendency to readily react withvarious substances with which it comes into contact and to thereby form undesirable products which may result in plugging of pipe lines, and to its detrimental effect on the anti-knock properties of the gasoline. I

Not only is the removal of fluorine from the hydrocarbon products important for the above reasons, but'also the decomposition of the combined fluorine compounds is important because the combined fluorine represents a loss of hydrogen fluoride since it is no longer available for use as the catalyst. It is a particular feature of the present invention that the treating agent herein disclosed functions to release hydrogen fluoride by decomposing the combined fluorine compounds, and the released hydrogen flubride may be recycled to the alkylation process for further use therein.

It is an object of the present invention to reduce the fluorine content of the hydrocarbon alkylation product to a pointwhere the adverse eflects are no longer substantial and to recover the hydrogen fluoride for further use in the alkylation process.

In abroad aspect the present invention relates to a process for purifying a hydrocarbon mixturesynthesized in the presence of an active fluoride catalyst and containing as an impurity a relatively small amount of organically combined fluorine, which comprises treating said hydrocarbon mixture with aluminum metal.

In one specific embodiment the present invention relates to a process for purifying an alkylation product formed in the presence of hydrogen fluoride and containing a relatively small amount of organically combined fluorine as an impurity, which comprises treating said alkylation product with etched aluminum rings.

While the present invention is particularly adapted to the removal of fluorine from normally liquid hydrocarbon mixtures, it is also applicable to treatment of normally gaseous hydrocarbons containing fluorine compounds as impurities therein.

According to the present invention, the alkylation product is contacted with aluminum metal.

For best results it is essential that certain factors in the use of the aluminum metal be given care ful consideration. These factors include the po rosity of the aluminum, its physical shape, the operating conditions under which the aluminum isemployed, etc.

Experiments have shown that a highly porous aluminum metal gives greatly improved results. A particularly suitable method of treating aluminum shapes to produce a porous product isto subject the aluminum metal to an etching treatment and this maybe accomplished by dipping in or otherwise suitably contacting the aluminum shapes with anacid such as muriatic acid, sulfuric acid, etc.

In the treatment of aluminum rings it has been found that a minimum of 6% of the total weight of the metal should be removed by the etching treatment since microscopic examinations have shown that etched ringsin which less than 6% of the total metal has been removed-are not as satisfactory as those in which a higher proportion of the metal has been so removed. As specific examples, muriatic acid of 2.4 to 0.6 normalcy may be employed at temperatures of 40 to F. The aluminum rings may be contacted with the acid for a period ranging from 7 minutes to 12 hours. In many cases it is beneficial to precede the acid treatment with a caustic treatment in order to remove surface coatings from the aluminum prior to the etching treatment.

' may comprise amalgamating aluminum shapeswith mercury followed by heating to a temperature of above about 850 'F. to remove the mer cury. Still another method may comprise pilling a mixture of fine aluminum granules or powder. It is understood thatthe aluminum shapes produced by these various methods are not necessarily equivalent. in their dehydrofluorinating.

activity.

Another important feature to be considered is" the physical shape of the aluminum. The aluminum should be in such shape that a large surface area is available for contact with the hydrocarbon mixture being treated. Aluminum rings are particularly preferred since they not only. meet the requirement of large surface area, but also are desirable as a fractionating means to be hereinafter described in detail. Satisfactory rings are those having diameters of from to 2", lengths of $5" to 2". and wall thicknessof to V Particularly preferred are aluminum rings of 1" tolt" diameter, 1" to 1%" length and 1"," wall thickness. Lessing rings of similar dimensions are also satisfactory. Aluminum rivets, aluminum turnings and aluminum granules have been used with satisfactory results. Another suitable treating agent may comprise carbon rings which have been sprayed with aluminum. It is understood that these aluminum shapes are preferably etched in the manner heretofore set forth.

It is also within the scope of the invention to use aluminum containing minor proportions of other metals. For example, aluminum-copper alloy rivets containing-2.2% copper have been sub- Jected to an etchingtreatment in the manner heretofore set forthand were then utilized as a catalyst .for dehydrofluorination. The alloy rivets were highly porous and gave very satisfactory results.

In the alkylation process. a hydrocarbon layer is separated from the catalyst layer and the hydrocarbonfllayer may then be fractionated to remove dissolved hydrogenfluoride. It is a particular feature of the present invention that the hydrocarbon layer may be subjected to said f ractionation inthe presence of the aluminum rings which may be disposed as a packing material in the fractionating zone. Thus the hydrogen fluoride produced by-the decomposition of the organically combined fluorine compounds may be separated and recovered'in cornmingled state with the hydrogen fluoride dissolved in the alkylation product. In such an operation, it is important that the shapeof the aluminum metal be such that it serves as a fractiona in means and thus may replace, in 'part or in whole, such contacting means as bubble trays 0r decks. baflle plates, side to side pans, etc. which normally are employed in conventional fractionation. The aluminum shape employed must be such that good vapor and liquid contact is'accomplished and also that free flow of vapor andliquid is permitted."

It is important that the temperature and pressure for optimum dehydrofluorination be correlated with the temperature and pressure for o'ptimuni'fractionation. so that both dehydrofluorination and fractionation are satisfactorily accomplished. The exact temperature, pressure and space velocity to be used will depend upon the particularmethod of operation employed. By space velocity, as used in the present specificatlon and claims, is meant the hourly liquid space velocity, defined as the volume of hydrocarbon mixture charged per volume of aluminum in the treating zone per hour.

In one embodiment of the invention, the alumi- I .5 num shapes may be disposed as packing material in a reaction zone and the hydrocarbon mixture passed therethrough under the desired temperature, pressure and space velocity. In this type of operation the temperature will usually be within 10 the range of from about 150 to about 600 F. and

' preferably of from about 200 to about 300 F.

- The pressure however is preferably sufficient to maintain the hydrocarbon in substantially liquid phase and thus the pressure may range from about substantially atmospheric to 500 pounds or more.

In the preferred method of operation the aluminum rings are disposed as packing material in a fractionating column which is provided with go means in the lower portion thereof for heating and with means provided in the upper portion thereof for cooling.- The hydrocarbon mixture to be treated may be introduced to the upper portion of the treating zone to flow downwardly 35 over the packlhg material, while contacting ascending vapors which have been formed by heating in the lower portion of the tower and by 'the heat exchange effected between the rising vapors and descending liquid at intermediate po- .30 sitions of the zone, thus continuously stripping hydrogen fluoride dissolved in the charge and formed by said decomposition and thereby separating the hydrogenfluoride from the hydrocarbons. This, in effect, comprises a plurality of vaporizing and condensing zones in the various sections of the dehydrofluorinating-fractionating zone. I

In the preferred type of operation the temperature may be within the range heretofore set forth, 0 but the pressure and space velocity must be correlated therewith in order to effect the desired fractionation. The exact conditions to be utilized will depend upon the character of the hydrocarbon material to be treated, the amount of dissolved hydrogen fluoride contained therein, the amount of combined fluorine compound, etc., but many event mixed vapor and liquid phases must be present.

One important advantage to the use'of aluminum as aldehydrofluorinating agent is that it decomposes the combined fluorine compounds and thus releases hydrogen fluoride which may be recycled to the alkylation zone for further use therein. This is advantageous overthe heretofore suggested dehydrofluorinating agents which combined chemically with the fluorine in the formation of a complex compound or which physically retain the fluorine, in any event not releasing the hydrogen fluoridefor reuse in the alkylation process. This highly important advantage in the decomposition of the organicallycombined fluorine compounds is particularly reflected in the preferred method'of operation in which dehydrofluorinating and fractionating occur in the same zone, because the hydrogen fluoride produced by said decomposition is removed from the fractionating zone shortly after it is formed and gasoline is essential in order to avoid the corrosive action of the fluorine compounds.

The following examples are introduced for the Pu pose of further illustrating the novelty and utility of the present invention but not with the intention of unduly limiting the same.

Example I Isobutane was alkylated by butenes in the presence of hydrogen fluoride catalyst at a temperature of 100 F. A hydrocarbon layer was separated from the catalyst layer and the hydrocarbon layer was then introduced into a stripping zone. The stripping zone comprised a vessel 7' long by 3" wide and was equipped with an internal closed coil in the lower portion thereof.

. than 10 mesh was disposed in the stripping zone and was supported therein 12 inches from the bottom by means of a perforated plate.

The hydrocarbon layer was passed downwardly through the stripping zone. The hydrogen fluoride liberated therein was removed from the upper portion of the 'stripping zone while the liquid hydrocarbons were removed from the lower portion thereof and were supplied to a stabilizing column.

The alkylate prior to introduction to the stripping zone had a fluorine content of about .01, while the fluorine content of the final alkylate as withdrawn from the lower. portion of the stabilizing column had a fluorine content of about 0.0001.

Example II A normal butane fraction containing 4.4% by weight of butyl fluoride was contacted with granular aluminum at a temperature of 240 F. under substantially atmospheric pressure. The product contained 0.064%, thus showing a reduction of 99% in a single pass.

Example III Example IV A synthetic mixture of normal butane and butyl fluoride containing 2000 parts per million of fluorine as determined by combustion and titration analysis was prepared. One portion of the synthetic mixture was contacted with aluminum rivets and another portion of the synthetic mixture was contacted with aluminum rivets which had been previously etched by first pretreating grams thereof with 4% potassium hydroxide for six minutes to remove surface coating and then by pickling in 180 cc. of hydrochloric acid until exhaustion of the acid. These tests were conducted at a temperature of 240 F. and a pressure of 330 pounds per square inch.

In the case of the aluminum rivets which had not been previously etched, the amount of de hydrofiuorination reached a maximum of only after flve hours inservice and then decreased, whereas with the etched aluminum rivets, the amount of dehydrofluorinationwas as high as after six hours of treatment and increased to 61% after seven hours.

The tests in this examplewere conductedby passing the charge through the treating agent under liquid phase conditions without simultaneous fractionation and therefore are not comparable with the results reported in the other examples, since the latter were'obtained from experiments employing concurrent dehydrofluorination and fractionation. A comparisonfof the results in this example with the results in the other examples further illustratesthe advantages of the preferred dehydrofluorinating-fractionating type of operation.

Example V The following experiments were conducted with an alkylation product containing 0.02 to 0.04% by weight of combined fluorine. The aluminum used was in the .form of turnings, aluminum rivets and aluminum sprayed carbon rings. For comparative purposes, experimental results on carbon rings are also included. The temperatures employed and the results obtained are shown in the following table.

- etched aluminum rivets are much better in this example than for the same treating agent in Example IV. The reason for this, as hereinbefore set forth, is that the tests in this example were conducted in concurrent dehydrofluorinatr ing and fractionating apparatus, whereas the experiments reported in Example IV were conducted without simultaneous fractionation.

In comparing the results obtained with the etched aluminum rivets and those obtained with the other treating agents, the difference in space velocities must be considered. It is noted that the experiments with the etched rivets were con-,

ducted at a space velocity of 6 as compared to a space velocity of 2 in the other tests.

I claim:

1. In the catalytic alkylation of hydrocarbons in the presence of hydrogen fluoride, wherein there is formed a hydrocarbon fraction containing a relatively small amount of an organic fluorine compound, the method which comprises contacting the hydrocarbon fraction with metallic aluminum to liberate hydrogen fluoride from said compound. separating thus liberated hydrogen fluoride from the hydrocarbon fraction and returning the same to the aikylation step.

2. In the catalytic alkylation of hydrocarbons in the presence of hydrogen fluoride, wherein there is formed a hydrocarbon liquid containing dissolved hydrogen fluoride andan organic fluorine compound, the method which comprises separating dissolved hydrogen fluoride from the hydrocarbon liquid by fractionating the latter .with copi r- 6,"!!! the catalytic alkylation of hydrocarbons r I 1, hydrogen fluoride together with said dissolved hydrogen fluoride separated by the fractionation, and'returning the separated hydrogen fluoride) to the alhlation step.

3. The method as deflned in claim 2 iurther characterized in that said aluminum has been made porousby etching.

4. The process asdeflned in claim 1 further made porous'by etching.

5 The process, as deflned in claim 1 further characterized in. that said aluminum is alloyed in'the presence of hydrogen fluoride, wherein there isi'ormed a hydrocarbon fractioncontaining a relatively small amount of an organic fluorine compound, the method which comprises characterized in that said aluminum has been contacting the hydrocarbon fraction with inetallic aluminum to liberate hydrogen fluoride irom'said compound. and separating the thus liberated hydrogen fluoride from said hydrocarbon fraction. I

'7.2l2n the catalytic alkylatlon of hydrocarbons in the presence of hydrogen fluoride, whereinthere is i'ormed a hydrocarbon liquid containing dissolved hydrogen fluoride and an organic fluorine compound, the method which comprises separating dissolved hydrogen fluoride-from the hydrocarbon liquid by iractionatlng the latter in the presence oi metallic aluminum whereby to liberate additional hydrogen fluoride from said organic compound, and separating said additional. hydrogen fluoride together with said dis- 7 solved hydrogen fluoride-from said hydrocarbon liquid.

GLENN u. wnnn. 'aaranrmcas crran The following references are of record in the flle of this patent:

UNITED STATES PATENTS Frey May 2, 1944 

